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表面工程诱导高熵合金纳米线的d带中心下调以增强纳米酶催化作用

Surface Engineering-Induced d-Band Center Down-Regulation in High-Entropy Alloy Nanowires for Enhanced Nanozyme Catalysis.

作者信息

Feng Kunyang, Wang Hanting, Zhou Song, Zhang Wei, Gong Chonghai, He Yuxin, Wang Yusen, Dai Wenchong, Li Jianbo, Zhang Zhengwei, Li Siqiao

机构信息

School of Basic Medical Sciences, Chongqing Medical University, Chongqing, 400016, China.

Chongqing Key Laboratory of Forensic Medicine, Chongqing Medical University, Chongqing, 400016, China.

出版信息

Adv Sci (Weinh). 2025 Jul;12(25):e2502354. doi: 10.1002/advs.202502354. Epub 2025 Apr 7.

DOI:10.1002/advs.202502354
PMID:40192189
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12224935/
Abstract

High-entropy alloys (HEAs) have garnered extensive attention owing to their broad compositional tunability and high catalytic activity. However, precisely modulating the enzyme-like activity of HEAs and enhancing their biocompatibility for biological applications remain severely challenging. Herein, PtRuFeCoNi HEA nanowires (NWs) are synthesized by adjusting the metal composition and surface-engineered with polydopamine (PDA) to form HEA NWs@PDA nanozymes (HEzymes@PDA) with superior catalytic activity and photothermal properties. Density functional theory calculations and the Sabatier principle reveal that self-polymerized PDA surface engineering moderately lowers the d-band center of the HEAs, optimizes the surface charge distribution, and enhances the adsorption-desorption efficiency of the substrates. As a proof-of-concept, the HEzymes@PDA are synergistically integrated with hydrogels for biosensing analysis. This study presents an innovative paradigm for designing highly active HEA nanozymes via surface engineering and demonstrates their immense potential in catalytic sensing applications.

摘要

高熵合金(HEAs)因其广泛的成分可调性和高催化活性而受到广泛关注。然而,精确调节高熵合金的类酶活性并提高其在生物应用中的生物相容性仍然极具挑战性。在此,通过调整金属成分合成了PtRuFeCoNi高熵合金纳米线(NWs),并用聚多巴胺(PDA)进行表面工程处理,以形成具有优异催化活性和光热性能的高熵合金纳米线@PDA纳米酶(纳米酶@PDA)。密度泛函理论计算和萨巴蒂尔原理表明,自聚合的PDA表面工程适度降低了高熵合金的d带中心,优化了表面电荷分布,并提高了底物的吸附-解吸效率。作为概念验证,纳米酶@PDA与水凝胶协同集成用于生物传感分析。本研究提出了一种通过表面工程设计高活性高熵合金纳米酶的创新范例,并展示了它们在催化传感应用中的巨大潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/ba544c38656d/ADVS-12-2502354-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/f63f2b0315c2/ADVS-12-2502354-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/e415b11bcaaf/ADVS-12-2502354-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/1b965a699011/ADVS-12-2502354-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/ba544c38656d/ADVS-12-2502354-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/f63f2b0315c2/ADVS-12-2502354-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/e415b11bcaaf/ADVS-12-2502354-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/1b965a699011/ADVS-12-2502354-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aa93/12224935/ba544c38656d/ADVS-12-2502354-g008.jpg

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本文引用的文献

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Fluorescent Fingerprint Identification of Protein Structural Changes and Disease-Specific Amyloid Beta Aggregates Based on a Single-Nanozyme Sensor Array.基于单纳米酶传感器阵列的蛋白质结构变化和疾病特异性淀粉样β聚集体的荧光指纹识别
Anal Chem. 2025 Mar 11;97(9):4978-4986. doi: 10.1021/acs.analchem.4c05508. Epub 2025 Feb 25.
2
Tailored Metal-Organic Framework-Based Nanozymes for Enhanced Enzyme-Like Catalysis.用于增强类酶催化的定制金属有机框架基纳米酶
Angew Chem Int Ed Engl. 2025 Feb 10;64(7):e202420200. doi: 10.1002/anie.202420200. Epub 2024 Nov 25.
3
Fine-Tuning the d-Band Center Position of Zinc to Increase the Anti-Tumor Activity of Single-Atom Nanozymes.
微调锌的 d 带中心位置以提高单原子纳米酶的抗肿瘤活性。
Adv Mater. 2024 Nov;36(48):e2412368. doi: 10.1002/adma.202412368. Epub 2024 Oct 13.
4
Surface Au-H Species as Self-Generated Prosthetic Groups of a Formate Dehydrogenase-like Au Nanozyme to Engineer Multienzymatic Activities.表面 Au-H 物种作为甲酸脱氢酶样 Au 纳米酶的自生成辅基,用于构建多酶活性。
ACS Nano. 2024 Sep 3;18(35):24162-24172. doi: 10.1021/acsnano.4c05516. Epub 2024 Aug 20.
5
Optimizing the standardized assays for determining the catalytic activity and kinetics of peroxidase-like nanozymes.优化用于测定类过氧化物酶纳米酶催化活性和动力学的标准化分析方法。
Nat Protoc. 2024 Dec;19(12):3470-3488. doi: 10.1038/s41596-024-01034-7. Epub 2024 Aug 15.
6
Atom-pair engineering of single-atom nanozyme for boosting peroxidase-like activity.原子对工程中单原子纳米酶用于增强过氧化物酶样活性。
Nat Commun. 2024 Aug 12;15(1):6888. doi: 10.1038/s41467-024-51022-4.
7
PdMoPtCoNi High Entropy Nanoalloy with d Electron Self-Complementation-Induced Multisite Synergistic Effect for Efficient Nanozyme Catalysis.具有 d 电子自补偿诱导多活性位协同效应的 PdMoPtCoNi 高熵纳米合金用于高效纳米酶催化。
Adv Sci (Weinh). 2024 Oct;11(38):e2406149. doi: 10.1002/advs.202406149. Epub 2024 Aug 9.
8
Artificial-Cofactor-Mediated Hydrogen and Electron Transfer Endows AuFe/Polydopamine Superparticles with Enhanced Glucose Oxidase-Like Activity.人工辅因子介导的氢和电子转移赋予 AuFe/聚多巴胺超粒子增强的葡萄糖氧化酶样活性。
Nano Lett. 2024 Aug 14;24(32):9974-9982. doi: 10.1021/acs.nanolett.4c02594. Epub 2024 Jul 31.
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